Process for the production of dyeings



Patented Dec. 30, 1941 PROCESS FOR. THE PRODUCTION OF DYEINGS William H.von Glahn, Loudonville, N. Y., assignorto General Aniline & FilmCorporation, a corporation of Delaware No Drawing. Application July9,1938, Serial No. 218,414. In Germany July 10, 1937 12 Claims.

The present invention relates to a new process for producing dyeings onfibrous material.

At the present time, several methods of applying azo dyestufls to fibersare known. One

consists in impregnating the fiber with an azo component, such asbeta-naphthol, the Naphthol-AS- compounds, and the like, andsubsequently developing the dyestufi by immersing the impregnated fiberin a bath containing a diazo compound. Another method, substantially thereverse of that described above, consists in applying a diazotizablesubstance to the fiber, subsequently diazotizing said substance on thefiber, and developing the dyestufl in a bath containing an azocomponent. v

A third and more recent method is that of impregnating the fiber with astabilized diazo com- .pound and an azo component and subsequently-forming the dye by treating the fiber with an acid to regenerate thefree diazo which immediately couples with the azo component. It has alsobeen suggested that the fiber may be treated with an aromatic base and adeveloper in one bath and diazotizing and coupling the two in a secondbath, care being taken to avoid precipitation or separation of thebases, developers or dyestuffs by employing a protective colloid in atleast one of the baths.

I have now found that excellent level dyeings may be obtained byimpregnating or printing on the fiber substantially water-insoluble butalkalisoluble aromatic bases capable of being dlazotized, together withan azo component, and developing the dyestuif on the fiber bysubsequently immersing the fiber in a bath containing nitrous acid so asto diazotize the base and. couple the diazo at the same time. Ascoupling compounds I may, for example, use the alkali-soluble naphthols,such as beta-naphthol and 2-hydroxynaphthalene-B-carboxylicacld-arylamide. Compounds, such as beta-keto-carboxylic acid-arylamide,are also useful.

As alkali-soluble, water-insoluble amines I prefer to employdiazotizable aromatic bases containing one or mor alkali-solubilizinggroups, such as sulfamido-, hydroxy groups, enolic hydroxy groups, orthe like.

Several types of the alkali-soluble but waterinsoluble bases which aresuitable for the present proce s are listed below:

(1) Amidoarylsulfonyl mono-alkylor andamides, such as compounds of theformulae:

NH: (0) ONE-s or? I HI B TE:

(3) Aromatic amines with an external sulfamid group, such as compoundsof the formula: CH3

(b) CHz-OSOrNH NH: 0 0 CH:

NH-SO wherein X stands for H, alkyl or aryl S OzNHX NH:

wherein X stands for H, alkyl or aryl,

(b) Aminobenzoyl-aminophenol N H: (c) Aminohydroxy-diphenylether QOGOH(5) Compounds having enolic hydroxy groups, such as:

' (a) Mono-acetoacetyl-phenylene-diamine (b)Aminobenzoylacetic-acid-arylide In practicing the present invention, thefiber may be treated with the base and the coupling component togetherwith the nitrite, whereupon the fiber is subjected to an acid treatmentto develop the dyestufi. It is also possible to treat the fiber with thetwo dyestuif components without the nitrite and subsequently subjectingthe impregnated fiber to treatment in a bath of nitrous acid. Thecoupling action usually takes place simultaneously with thediazotization. It is often desirable to complete the coupling by partlyor entirely neutralizing the acid or even finally rendering the bathalkaline; this may, for example, be effected by aftertreatment withbasic reacting agents, such as ammonia vapor or alkaline solutions.

The following examples serve to illustrate the invention, but it is notintended to limit the invention specifically thereto:

Example 1.1.33 grs. of 1-amino-4-methyl-3- sulfanilido benzene of theformula:

and 0.72 gr. of beta-naphthol are dissolved in mersed for from'ten tofifteen'minutes at room for from ten to fifteen minutes and thenimtemperature in 500 cc. of water containing 3.5 grs. of sodium nitriteand 7 cc. of glacial acetic acid. The material is then washed and dried.A bright orange shade is obtained.

By carrying out the development at a temperature of from 70 to C.instead of at room temperature, a full bright orange shade is obtainedimmediately.

Example 2.1.33 grs. of 1-amino-4-methyl-3- sulfanilido benzene and 1.55grs. of 2-hydroxy-3- (2'-ethoxybenzene) carbonylamido naphthalene aredissolved in- 15 cc. of water, 1 cc. of monopol oil and 2 cc. of causticsoda solution of 40% by volume. 50 grs. of a neutral tragacanththickener and enough water are added to the solution to make up grams.

The paste is printed onto. acetate silk, the printed silk is dried andthen steamed'for from ten to fifteen minutes. It is then immersed forfrom ten to fifteen minutes at room temperature in a bath containing 7grs. of sodium nitrite and 14 grs. of glacial acetic acid per liter ofwater. The material is then washed and dried. A scarlet shade isobtained, the dyestuif having the following formula:

CH OCgHs C ONH The dyestuif may also be developed at a temperature of 75C.

An application of this process to regenerated cellulose and wool willalso render level dyeings when the development is carried out at roomtemperature or at 75 C.

Example 3.-1 gr. of 1-amino-4-methyl-3- sulfanilido benzene and 1 gr. of2-hydroxy-3-(3- nitro benzene) carbonylamido naphthalene are dissolvedin water with 5 cc. of ethyl alcohol, 5 cc. of monopol brilliant oil, 1cc. of caustic soda solution of 40% by volume. This solution is broughtto one liter with water and 25 grs. of Glaubers salt.

Acetate crepe silk is impregnated therewith by placing it in thissolution for from one to three hours, at a temperature of from 60 to 70C. The material is then rinsed and treated for twenty minutes in a bathcontaining 2 grs. of sodium nitrite and 5 cc. of concentratedhydrochloric acid per liter, whereupon the diazotization and thecoupling are effected simultaneously. Thereafter, the dyeing is treatedfor a half hour with a soap solution (5 grs. of soap per liter) at 30 C.A yellowish-red is obtained which has the following formula:

0H NOq Example 4.1 gr. of 1-amino-6-methoxy-3- methyl-sulfamido benzeneand 1 gr. of 3-hydroxy-2-(2'.5'-dimethoxy benzene) carbonylamidodiphenylene oxide are dissolved in water with cc. of ethyl alcohol, 5cc. of monopol brilliant oil and 1.5 cc. of caustic soda solution of 40%by volume. This solution is brought to one liter with water and 25grs.of Glaubers salt.

grs. of acetate silk are impregnated with 300 cc. of this solutionforon-e hour at a temperature of from 60 to 70 C. After a short rinsing,the material is treated in a bath containing 2 grs. of sodium nitriteand 5 cc. concentrated hydrochloric acid per liter, whereupondiazotization and a weak coupling action are effected. In order tocomplete the development, the material is treated for ten minutes at atemperature of 70 C. in a second bath containing 5 grs. of sodiumacetate per liter. After treatment with a soap solution, a brown shadeis obtained, the dyestuif having the following formula:

CONH

OCHs

Example 5.-.,-1 gr. of 1-methy1-2(2'-hydroxynaphthalene 3'-carbonylamino) 5 methoxybenzene and 1 gr. ofdi(-4-methyl-3-aminobenzene-sulfonylamino) -ethane are dissolved inwater with 5 cc. of alcohol, 5 cc. of monopol oil and 2.5 cc. of causticsoda solution (1:10). This solution is brought to one liter with waterand 25 grs. of Glaubers salt.

By proceeding in the same manner as described in Example 4, acetate'silk is dyed a full orange shade.

Example 6.A printing paste is made up in a manner similar to thatdescribed in the preceding examples, with the following constituents:

And a sufflcient quantity of water to make a total weight of 100 grams.This printing paste may be printed upon wool, acetate silk orregenerated cellulose. After drying the material, it is treated with asolution containing 250 cc. of hydrochloric acid (22 B.), 500 grs. oftragacanth (65:1000), 10 cc. formaldehyde solution and a suflicientquantity of water to make a total weight of 1000 grams, aerated, andsubsequently treated at a temperature of 50 C. in a bath containing 30grs. of calcined soda per liter of water. The material is thereuponrinsed, treated with a soap solution, again rinsed and dried. A brownshade is obtained, the dyestuff having the following general formula:

cum-Q-somn-om I N I -on CONlI-C Cl grs. of glacial acetic acid perliter, whereupon the diazotization of the base'and the develop- 'ilidonaphthalene.

ment of the dyestuff is effected. A red-violet shade is obtained, thedyestuff having the following formula:

Example 8.--A printing paste is prepared in the manner described inExample 2 by employing 1.94 grs. of 1.4-diethoxy-2-amino-5-(2'-hydroxy-5'-chlorbenzene) carbonylamido benzene and 1.3 grs.'of2-hydroxy-3-carbonyl-an- The paste may be printed upon wool, acetatesilk, and regenerated cellulose. After drying the material, it istreated at room temperature in a bath containing? grs.

, of sodium nitrite and 14 grs. of glacial acetic acid per liter,whereupon the diazotization of the base and the development of thedyestuff are eifected. A blue shade is obtained, the dyestuff having thefollowing formula:

| F Q C21150 c1 0 can Example 9.1.4 grs. of para-amino benzenesulfo-ortho-anisidid of the formula:

OCH:

and 1.47 grs. of Naphthol-AS-OL are dissolved, made into a printingpaste. printed and developed as in Example 1. A clear scarlet shade isproduced. I

Example 10.-1.5 grs. of l-amino-naphtha- 1ene-4-su1fanilid of theformula:

and 1.39 grs. of Naphthol-AS-D are dissolved, made into a printingpaste, printed and developed as in Example 1. A deep clear bluish-redshade is obtained.

If the development is carried out at atemperatiu'e of from 70 to 80 C.,the full shade is developed immediately.

Example 11.1.46 grs. of l-para-toluoIl-sulfonylamido-2-metl'ioxy-4-aminobenzene of the formula:

O CH:

and 1.32 grs. of Naphthol-AS are dissolved; made into a printing paste,printed and developed as in Example 1. A strong reddish-brown shade isobtained.

Example 12.1.32 grs. of 4-amin0-benzene sulfo-4'-amino-anilide of theformula;

nm-O-s OzNHONHs and 1.32 grs. of Naphthol-AS are printed as inExample 1. A'brilliant orange shade is obtained.

Example 13.1.5 grs. of 4-amino-benzenesulfo-e-naphthyl-amide of theformula:

and 1.7 grs. of Naphthol-AS-LB are printed as in Example 1. A brightbrown shade is obtained. I

If 1.54 grs. of Naphthol-AS-PH are used instead, a deep reddish-brownshade is obtained.

Example 14.--1.31 grs. of 1-amino-4-methylbenzene-S-sulfanilid of theformula:

and 1.54 grs. of Naphthol-AS-PH are dissolved 10 in 300 cc. of water, 3cc. of caustic soda of 40% 15 sodium nitrite and 2% glacial acetic acid,for

about fifteen minutes at about room temperature, whereupon thediazotization and development of the dyestufi is eifected. A scarletshade is produced.

If the silk is dyed at a temperature of from to C. and then subjected totreatment in'the nitrite acid bath at 70 to C. instead of at roomtemperature, the dyestuff is developed and a shade of the same depth isobtained immediately.

Example 15.-1.31 grs. of 1-amino-4-methylbenzene-3-sulfanilid and 1.7grs.'of Naphthol- AS-LB are dissolved as in Example 1 and the solutionis diluted with water and cellosolve to make up 300 ccs. 10 grs. ofcotton are immersed in this bath for fifteen minutes, the material issqueezed off, and the dyestuff is developed by treatment in a bath,containing 1% sodium nitrite and 2% glacial acetic acid, for from ten tofifteen minutes at room temperature. A yellowi sh-brown shade isobtained.

If the dyeing and developing is carried out at a temperature of from 70to 80C., a similar shade of equal depth is obtained in much less time.

If 10 grs. of rayon are dyed and developed as I described above, a deepbrown shade is obtained.

Example 16.2.1 grs. of 1.4-disulfani1ido-2- aminobenzene of the formula:

and 1.32 grs. of Naphthol-AS are printed and developed as described inExample 15. A clear orange shade is obtained.

Several further combinations are listed in the following table. Thedevelopment of the dyestuffs takes place in the manner described in theexamples.

Base Coupling component Shade Para-aminobenzene sulfo-ortho-anisidid2-hydroxy-3-(2-methoxy benzene) carbonyl- Scarlet.

. amido naphthalene.

... fl-naphthol Orange.

2-hydroxy-3-carbonyl-anilido naphthalune.. R d

carbonylamido carbazole e Yellow-brown.

3.3-dimethyl-4.4-di-(acetoacetylamino) di- Yellow.

. phenylene.

do Do.

2-hydroxy- 3-(2.5-di methoxybenzene) car- Yellowish-red.

bonylamido naphthalene.

Z-hydroxy-ii-(ortho-toluene) carbonylamido 'Bluish-red.

naphthalene.

2-hydroxy-3-(4-chloro-benzene) carbonyl- Brown.

amid carbazole o -l1ydroxy-3'-uaphthalene carbonylamldo ben- Zeno.

Strong reddish-brown Base Coupling component Shade 4-methylbenzenesulfo-4'-emidoanilide 2-hydi ofi y-il-(wethoxybenzene) cerbonylamldoGolden yellow.

nap e ene. Z-methoxy-i-amlno-S-methyl benzene sulfeni- 2-hydroxy-3-2'-methoxy-benzene) carbonyl- Reddlsh Bordeaux.

lide. amldo nap thelene.

Do 2-hydroxy-3-(2- ethyl-4'-methoxybenzene) D0.

. carbonylemldo-naphthalene. 1-para-toluene-sultonylamido-2-methyl-4-2-hydroxysi-(ortho-toluene) cerbonylemido Yellowish red.

(meta-amino-para-methoxybenzoyl-amino)- naphthalene. o-acetyl benzene.3-(para-arfiinombenzoyl-amino)'d-methylben- 2-hydroxy-3-cerbonyl-anilidonaphthalene. Red.

zene so am 1 e. l-hydroxy-4-(2-emino-benzoyl-methylamino)-2-hydroxy-8-(ortho-toluene) cerbonylemido Golden orange.

benzene. naphthalene. l.i-dlethoxy-2-amino-5-(2'-hydroxy-4'-methyl-2-hydroxy-3-carb0ny1-an1lid0 nephthalene Blue.

benzoylamlno)-benzene. l-methoxy-2-(2'-hydroxy-3'-methylbenzoyl-2-hydroxy-3-(ortho-toluene) carbonylamido Reddish-blue.aminol-4-phenoxy-5-emino benzene. naphthalene.l-rnethoxy-2-amino-4-phenoxy-5-(2hydroxy-5 2-hydroxy-3-(ortho-toluene)carbonylarnldo Do. methylbenzoylamino)-benzene. naphthalene.1.4-diethyl-2-an1ino-5-acetoacetylamino-ben- 2-hydgiigis-(ortho-toluene)carbonylamido Reddish-blue-black..

zene. nap ene. 1-(2.5'-dimethoxy-ifeminobenzene sullonyldo Bluish-red.

amino)-4-methoxybenzene. Do 2-hydroxy-3-(2-methoxybenzene) carbonyl-Red.

amide naphthalene. Di-(4-methyl-3-amino-benzene sulionylamino)2-hydroxy-3-(4-methoxybenzene) carbonyl- Orange.

ethane. amido naphthalene Do 2-hydroxy-3-(2'.5"dimethoxy-benzene)cerbon- Reddishorange.

ylamido naphthalene.

I claim: are in contact with the acetate matenal, to there- I. Processof dyeing fibrous material which 7 comprises applying to the fibrousmaterial aqueous alkaline solutions of both a diazotizable,water-insoluble aromatic amine containing in the molecule analkali-solubilizing radical selected from the group consisting of SOzNH,enolic hydroxy radicals and phenolic hydroxy' radicals and a couplingcomponent and then diazotizing said amine and coupling the diazotizedamine with the coupling component while said compounds are in contactwith the fibrous material, to thereby develop an azo dyestuff on thefibrous material. 7

2. Process of dyeing acetate material which comprises applying to theacetate material aqueous alkaline solutions of both a diazotizable,water-insoluble aromatic amine containing in the molecule analkali-solubilizing radical selected from the group consisting of SOzNH,enolic hydroxy radicals and phenolic hydroxy radicals and a couplingcomponent and then diazotizing said amine and coupling the diazotizedamine with the coupling component while said compounds are in contactwith the acetate material, to thereby develop an azo dyestufi on theacetate material.

3. Process of printing textile material which comprises applying to saidtextile material a printing paste containing a diazotizable,waterinsoluble aromatic amine containing in the molecule analkali-solubilizing radical selected from the group consisting ofSOzNI-I, enolic hydroxy radicals and phenolic hydroxy radicals, acoupling component and an alkali, diazotizing said amine and couplingthe diazotized amine with the coupling component while said compoundsare in contact with the textile material, to thereby develop an azodyestufif on the fibrous material.

4. Process of printing acetate material which comprises applying to saidacetate material a printing paste containing a diazotizable,waterinsoluble aromatic amine containing in the molecule analkali-solubilizing radical selected from the group consisting of SOzNH,enolic hydroxy radicals and phenolic hydroxy radicals, a couplingcomponent and an alkali, diazotizing said amine and coupling thediazotized amine with the coupling component while said compounds bydevelop an azo dyestuff on the acetate material.

5. A printing paste comprising a diazotizable, water-insoluble aromaticbase containing in the molecule an alkali-solubilizing radical selectedfrom the group consisting of SOzNH, enolic hydroxy radicals and phenolichydroxy radicals, a coupling component and an alkali.

6. Process of dyeing fibrous material which comprises applying to thefibrous material aqueous alkaline solutions of both an alkali-soluble,water-insoluble diazotizable amino-sulfarylid and a coupling componentand then diazotizing said sulfraylid and coupling the diazotizedsulfarylid with the coupling component while said compounds are incontact with the fibrous material, to thereby develop an azo dyestuff onthe fibrous material. 7

7. Process of dyeing acetate material which comprises applying to theacetate material aqueous alkaline solutions of both an alkali-soluble,water-insoluble diazotizable amino-sulfarylid and a coupling componentand then diazotizing said sulfarylid and coupling the diazotizedsulfarylid with the coupling component while said compounds are incontact with the acetate material, to thereby develop an azo dyestufi onthe acetate material.

8. Process of printing textile material which comprises applying to saidtextile material a printing paste containing an alkali-soluble,water-insoluble diazotizable amino-sulfarylid, a coupling component andan alkali, diazotizing said sulfarylid and coupling the diazotizedsulfarylid with the coupling component while said compounds are incontact with the textile material, to thereby develop an azo dyestufi onthe fibrous material.

9. Process of printing acetate material which comprises applying to saidacetate material a- 10. A printing paste comprising an alkali-soluble,water-insoluble diazotizable amino-sulfarylid, a coupling component andan alkali.

11. Process of printing textile material which comprises applying tosaid textile material a printing paste containing an alkali-soluble,water-insoluble diazotizable amino-sulfarylid, a coupling component. analkali-metal nitrite and an alkali, diazotizing said sulfarylid andcoupling

